EP1664363B1 - Corps en metal dur ou en cermet et procede de fabrication - Google Patents

Corps en metal dur ou en cermet et procede de fabrication Download PDF

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Publication number
EP1664363B1
EP1664363B1 EP04732930A EP04732930A EP1664363B1 EP 1664363 B1 EP1664363 B1 EP 1664363B1 EP 04732930 A EP04732930 A EP 04732930A EP 04732930 A EP04732930 A EP 04732930A EP 1664363 B1 EP1664363 B1 EP 1664363B1
Authority
EP
European Patent Office
Prior art keywords
mass
volume
layer
binder
metals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP04732930A
Other languages
German (de)
English (en)
Other versions
EP1664363A1 (fr
Inventor
Walter Lengauer
Vera Ucakar
Klaus Dreyer
Dieter Kassel
Hans Werner Daub
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kennametal Widia Produktions GmbH and Co KG
Original Assignee
Kennametal Widia Produktions GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kennametal Widia Produktions GmbH and Co KG filed Critical Kennametal Widia Produktions GmbH and Co KG
Priority to PL04732930T priority Critical patent/PL1664363T3/pl
Publication of EP1664363A1 publication Critical patent/EP1664363A1/fr
Application granted granted Critical
Publication of EP1664363B1 publication Critical patent/EP1664363B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B22F3/101—Changing atmosphere
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • the invention relates to a hard metal or cermet body having a hard material phase of WC and at least one carbide, nitride, carbonitride or oxicarbonitride of at least one of the elements of the IVa or Va group of the periodic table and having a binder phase of Fe, Co and / or Ni whose Proportion is 3-25 mass%.
  • a nitriding treatment of the cemented carbide below the melting temperature of the binder phase can be carried out, the mixture then being heated up to the sintering temperature under vacuum.
  • the nitrogen required for the nitridation can be supplied to the cemented carbide mixture batch both by a nitrogen atmosphere used and in the form of nitrides or carbonitrides of one of the hard material carbides.
  • the sintering is introduced under vacuum so that the gradient zone formation can occur.
  • the gradient zone can also be obtained by subjecting the cemented carbide, after sintering in the temperature range from about 1150 to at most 1300 ° C., to a nitrogen treatment under elevated pressure.
  • the sintering of the hard metal by dewaxing to 600 ° C, holding, heating to sintering temperature and subsequent vacuum sintering at 0.1 to 100 Pa and then Drucksintem done.
  • the sintered body of a pressure treatment with a nitrogen at 1 to 10 MPa and a subsequent vacuum treatment at 10 to 100 Pa subjected.
  • the US 4,276,096 describes a process for the production of carbide bodies of increased wear resistance, consisting of at least one of the binder metals Fe, Co and Ni, and one or more carbides of the elements Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W by Sintered and after the final sintering for at least 15 minutes at temperatures between 800 ° C and an upper temperature which is at least 50 ° C below the maximum sintering temperature, a nitrogen-containing atmosphere under a pressure between 2 x 10 5 Pa and 5 x 10 8 Be exposed to Pa.
  • the wear resistance of such carbide or cermet body is to be improved, which are used as cutting tools.
  • This cemented carbide or cermet body has, beneath a 2 to 100 ⁇ m thick first layer with increased binder content and a reduced proportion of mixed carbides, a further 2 to 40 ⁇ m thick second layer which has a higher nitrogen content than the first layer and which consists essentially of nitrides and and / or carbonitrides of the metals of the IVa group of the Periodic Table and phase proportions of up to 10% by volume of carbides, nitrides, carbonitrides or oxycarbonitrides of the elements W, Mo, V, Ta, Nb, Cr and / or dissolved in the hard material phases of up to 5 mass% V, Nb, Ta and up to 2 mass% of Cr, Mo, W and containing up to 15 mass% of binder.
  • this second layer is a transition zone having a thickness of 2 to 100 ⁇ m, in which the composition gradually changes to a homogeneous composition in the interior of the cemented carbide or cermet body.
  • a relatively tough and abrasive resistant zone is given with high levels of WC
  • underlying layer is a diffusion-resistant, hard layer with high nitride or carbonitride proportions.
  • said first layer has only up to 2% by mass of carbides or carbonitrides of at least one of the metals V, Nb, Ta and / or Cr.
  • the first layer has a composition consisting of 4 to 15 mass% or 7 to 22 volume% binder metal (s), 80 to 96 mass% or 66 to 93 volume% WC and 0 to 5 mass% or 0 to 12 volume% TiCN and / or TiN.
  • the total amount of the aforementioned substances gives 100 mass% or 100 volume%.
  • the second layer preferably has 3 to 15 mass% or 2 to 15 volume% binder metal (s), 0 to 50 mass% or 0 to 30 volume% WC and 35 to 98 mass% or 55 to 98 volume% TiCN or TiN, wherein the total amount of binder metal, WC and TiCN and / or TiN is 100 mass% or 100 volume%.
  • the nitrogen content in said second layer is from 8 to 22 mass% when the nitrides in that layer are present exclusively as metal nitrides.
  • the nitride level decreases in the presence of metal carbonitrides as nitrogen is replaced by carbon.
  • the nitrogen content of the second layer is thus preferably minimized to one-half, that is. on 4 to 22 mass%.
  • the hard metal or cermet body can additionally have a single-layer or multi-layer coating on at least one surface.
  • This coating can consist of carbides, nitrides, carbonitrides, oxides, oxinitrides of the elements of the IVa-Vla group of the Periodic Table, but also Al 2 O 3 , ZrO 2 , HfO 2 , AION or carbon, preferably as diamond or molybdenum or tungsten sulfides ,
  • the number of additional layers applied for example by means of PVD or CVD, and the choice of layer compositions depend on the intended use.
  • the cemented carbide or cermet body produced by powder metallurgy is subjected to a heat treatment after sintering or during the sintering of a first heat treatment to produce a binder metal-enriched 2-100 ⁇ m thick layer and then additionally subjected to this heat treatment of a nitrogen atmosphere under a nitrogen pressure of 50 mbar (5 ⁇ 10 3 Pa). to 100 bar (10 7 Pa) below the eutectic, preferably treated at 1000 ° C to 1200 ° C.
  • the binder metal enriched and mixed carbide depleted first layer remains in its composition in
  • the first near-surface layer has accordingly the effect of a membrane that allows nitrogen to pass from outside to inside simultaneously inhibits diffusion of nitrogen-affine metals to the outside.
  • this membrane-like effect occurs only in a temperature range below the eutectic, namely at 1000 to 1200 ° C.
  • titanium or other nitrogen-affine metals diffuse in the direction of the substrate body surface, where they form corresponding nitrides in the near-surface edge zones.
  • the nitrogen diffusion slows down, so that the desired effect of nitrogen enrichment in the second layer practically no longer occurs. Compliance with the temperature limits in the second heat treatment is thus crucial for the success of the method according to the invention.
  • the resulting layer below at least one surface by grinding, etching or other methods to remove before the body in a nitrogen atmosphere under a Nitrogen pressure 5 x 10 3 Pa to 10 7 Pa below the eutectic, preferably at temperatures between 1000 ° C and 1200 ° C is treated.
  • a nitrogen-enriched, 2 to 40 ⁇ m thick layer with a higher nitrogen content forms immediately below the surface.
  • This method can be used in particular for those substrate bodies which serve as cutting tools, wherein below the free surface the layer sequences a) to c) described in claim 1 are present, while on the chip surface or at least in the region of the rake face near the cutting edge, only one layer sequence according to b) and c) or claim 3 is present.
  • the life in continuous section measured by the wear mark width and the Kolktiefe could be increased by 8 to 10 times.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Powder Metallurgy (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Ceramic Products (AREA)
  • Adornments (AREA)
  • Chemical Vapour Deposition (AREA)

Claims (6)

  1. Corps en métal dur ou en cermet avec une phase de substance dure en WC et au moins un carbure, nitrure, carbonitrure ou oxycarbonitrure d'au moins un des éléments du groupe IVa ou Va de la classification périodique des éléments ainsi qu'avec une phase liant en Fe, Co et/ou Ni dont la proportion est comprise entre 3 et 25 % en masse, au-dessous de l'unique ou d'au moins une des surfaces
    a) étant disposée une première couche d'une épaisseur comprise entre 2 et 100 µm qui présente une proportion de métal liant comprise entre 2 et 25 % en masse et jusqu'à 25 % en volume de nitrures ou carbonitrures d'un métal ou de plusieurs métaux du groupe IVa de la classification périodique des éléments et/ou jusqu'à 10 % en volume de carbures et/ou de carbonitrures de V, Nb, Ta et/ou Cr, reste WC, la quantité des nitrures, carbonitrures ou carbures des métaux susmentionnés étant d'au moins 0,01 % en volume,
    b) au-dessous de la première couche étant disposée une deuxième couche d'une épaisseur comprise entre 2 et 40 µm et ayant une proportion d'azote supérieure à celle de ladite première couche, cette deuxième couche se compose de nitrures et/ou de carbonitrures des métaux du groupe IVa de la classification périodique des éléments et possède des proportions de phase allant jusqu'à 10 % en volume de carbures, nitrures, carbonitrures ou oxycarbonitrures des éléments W, Mo, V, Ta, Nb, Cr et/ou des proportions dissoutes dans la phase de substance dure qui vont jusqu'à 5 % en masse de V, Nb, Ta et jusqu'à 2 % en masse de Cr, Mo, W et comprend jusqu'à 15 % en masse de liant, la quantité des proportions de phase susmentionnées étant d'au moins 0,01 % en volume et/ou la quantité des proportions susmentionnées dissoutes dans la phase de substance dure étant d'au moins 0,01 % en masse,
    c) au-dessous de ladite deuxième couche étant disposée une zone de transition d'une épaisseur comprise entre 2 et 100 µm dans laquelle la composition change graduellement de manière à avoir une composition homogène à l'intérieur du noyau du corps en métal dur ou en cermet.
  2. Corps en métal dur ou en cermet selon la revendication 1, caractérisé par le fait que ladite première couche selon a) présente jusqu'à 2 % en masse de carbures ou de carbonitrures de l'un des métaux V, Nb, Ta et/ou Cr.
  3. Corps en métal dur ou en cermet selon la revendication 1 ou 2, caractérisé par le fait que ladite première couche selon a) comprend
    entre 4 et 15 % en masse ou entre 7 et 22 % en volume de métal (métaux) liant(s),
    entre 80 et 96 % en masse ou entre 66 et 93 % en volume de WC et
    entre 0 et 5 % en masse ou entre 0 et 12 % en volume de TiCN et/ou de TiN,
    les quantités totales de métaux liants, WC et TiCN et/ou TiN donnant 100 % en masse ou bien 100 % en volume.
  4. Corps en métal dur ou en cermet selon l'une quelconque des revendications 1 à 3, caractérisé par le fait que ladite deuxième couche selon b) comprend
    entre 3 et 15 % en masse ou entre 2 et 15 % en volume de métal (métaux) liant(s),
    entre 0 et 50 % en masse ou entre 0 et 30 % en volume de WC et
    entre 35 et 98 % en masse ou entre 55 et 98 % en volume de TiCN et/ou de TiN,
    les quantités totales de métal liant, WC et TiCN et/ou TiN donnant 100 % en masse ou 100 % en volume.
  5. Corps en métal dur ou en cermet selon l'une quelconque des revendications 1 à 4, caractérisé par le fait que la teneur en azote dans la deuxième couche selon b) est comprise entre 8 et 22 % en masse lorsque des nitrures liés présents dans cette couche se présentent exclusivement en tant que nitrure de métal et que la teneur en azote diminue proportionnellement au fur et à mesure de la proportion à laquelle des atomes d'azote sont remplacés en carbonitrures de métal.
  6. Corps en métal dur ou en cermet selon l'une quelconque des revendications 1 à 5, caractérisé par le fait qu'une surface au moins présente un revêtement à une ou plusieurs couche(s), se composant de carbures, nitrures, carbonitrures ou oxynitrures des éléments des groupes IVa à VIa de la classification périodique des éléments, d'Al2O3, de ZrO2, d'HfO2,d'AION ou de carbone, de préférence de diamant ou de Mo ou de sulfures de W.
EP04732930A 2003-09-12 2004-05-14 Corps en metal dur ou en cermet et procede de fabrication Expired - Lifetime EP1664363B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04732930T PL1664363T3 (pl) 2003-09-12 2004-05-14 Korpusy z twardych stopów lub cermetu i sposób ich wytwarzania

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10342364A DE10342364A1 (de) 2003-09-12 2003-09-12 Hartmetall-oder Cermetkörper und Verfahren zu seiner Herstellung
PCT/DE2004/001016 WO2005026400A1 (fr) 2003-09-12 2004-05-14 Corps en metal dur ou en cermet et procede de fabrication

Publications (2)

Publication Number Publication Date
EP1664363A1 EP1664363A1 (fr) 2006-06-07
EP1664363B1 true EP1664363B1 (fr) 2010-08-25

Family

ID=34305731

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04732930A Expired - Lifetime EP1664363B1 (fr) 2003-09-12 2004-05-14 Corps en metal dur ou en cermet et procede de fabrication

Country Status (8)

Country Link
US (1) US7544410B2 (fr)
EP (1) EP1664363B1 (fr)
JP (1) JP2007505212A (fr)
CN (1) CN100439535C (fr)
AT (1) ATE478969T1 (fr)
DE (2) DE10342364A1 (fr)
PL (1) PL1664363T3 (fr)
WO (1) WO2005026400A1 (fr)

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Publication number Priority date Publication date Assignee Title
ATE438600T1 (de) * 2005-11-17 2009-08-15 Boehlerit Gmbh & Co Kg Beschichteter hartmetallkörper
JP5187572B2 (ja) * 2008-07-09 2013-04-24 三菱マテリアル株式会社 ダイヤモンド被覆超硬合金製切削工具
DE102008048967A1 (de) 2008-09-25 2010-04-01 Kennametal Inc. Hartmetallkörper und Verfahren zu dessen Herstellung
US8663359B2 (en) * 2009-06-26 2014-03-04 Dimicron, Inc. Thick sintered polycrystalline diamond and sintered jewelry
CN102560393B (zh) * 2010-12-27 2016-04-06 青岛韬谱光学科技有限公司 镀膜件
US8574728B2 (en) 2011-03-15 2013-11-05 Kennametal Inc. Aluminum oxynitride coated article and method of making the same
AT510981B1 (de) * 2011-03-18 2012-08-15 Boehlerit Gmbh & Co Kg Beschichteter körper, verwendung desselben und verfahren zu dessen herstellung
GB201105150D0 (en) * 2011-03-28 2011-05-11 Element Six Holding Gmbh Cemented carbide material and tools comprising same
EP2725111B1 (fr) * 2011-06-27 2019-10-02 Kyocera Corporation Alliage dur et outil de coupe
US8834594B2 (en) 2011-12-21 2014-09-16 Kennametal Inc. Cemented carbide body and applications thereof
DE102012018067A1 (de) * 2012-09-13 2014-03-13 Tutec Gmbh Hexagonales WC-Pulver, Verfahren zu dessen Herstellung sowie Verwendung dieses Pulvers
US9017809B2 (en) 2013-01-25 2015-04-28 Kennametal Inc. Coatings for cutting tools
US9138864B2 (en) 2013-01-25 2015-09-22 Kennametal Inc. Green colored refractory coatings for cutting tools
US9427808B2 (en) 2013-08-30 2016-08-30 Kennametal Inc. Refractory coatings for cutting tools
JP6327102B2 (ja) * 2014-10-10 2018-05-23 新日鐵住金株式会社 超硬工具
JP5989930B1 (ja) * 2014-11-27 2016-09-07 京セラ株式会社 サーメットおよび切削工具
JP6614491B2 (ja) * 2014-12-25 2019-12-04 三菱マテリアル株式会社 複合焼結体切削工具および表面被覆複合焼結体切削工具
CN104862637A (zh) * 2015-05-09 2015-08-26 芜湖鼎瀚再制造技术有限公司 Co-ZrO2-HfO2纳米涂层材料及其制备方法
CN107614719B (zh) * 2015-06-12 2019-05-07 株式会社泰珂洛 硬质合金和被覆硬质合金
CN105112756A (zh) * 2015-08-12 2015-12-02 蔡婷婷 一种碳氮化钛复合氧化铝金属陶瓷刀具材料及其制备方法
CN106312048A (zh) * 2016-09-18 2017-01-11 广东工业大学 一种金属陶瓷颗粒及其制备方法与应用

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Also Published As

Publication number Publication date
PL1664363T3 (pl) 2011-02-28
JP2007505212A (ja) 2007-03-08
US7544410B2 (en) 2009-06-09
WO2005026400A1 (fr) 2005-03-24
CN100439535C (zh) 2008-12-03
ATE478969T1 (de) 2010-09-15
EP1664363A1 (fr) 2006-06-07
US20070042222A1 (en) 2007-02-22
DE10342364A1 (de) 2005-04-14
CN1820089A (zh) 2006-08-16
DE502004011588D1 (de) 2010-10-07

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